The hydrodefluorination of CF3-substituted alkenes can be catalyzed by a nickel(II) hydride bearing a pincer ligand. The catalyst loading can be as low as 1 mol%. gem-Difluoroalkenes containing a number of functional groups can be formed in good to excellent yields by a radical mechanism initiated by H center dot transfer from the nickel hydride. The relative reactivity of various substrates supports the proposed mechanism, as does a TEMPO trapping experiment.